Textile sizing composition



Patented Jan. 31, 1950 TEXTILE SIZING COMPOSITION George D. Jefferson,Kennett Square, Pa., and

Richard D. to Atlas Powder Fine,- Merchantville, N. 1., assignorlCompany. Wilmington, Del, a corporation of Delaware No Drawing.Application December 17, 1946. Serial No. 716.878

" 13 Ell-hill.- (Cl. 260-285) The present invention relates to a textilesis:

ing composition.

An object of the invention is to provide a composition which isparticularly useful for sizing nylon yarn preparatory to a knittingoperation.

Another object is to provide an improved sizing composition of'the typecomprising boric acid and a water-sensitive polyvinyl e A further objectis' to provide iirdry form and readily water-dispersible a sizingcomposition comprising boric acid and a water-sensitive polyvinyl resin.

Another object is to provide a sizing composition, particularly fornylon yarns, which combines the known valuable properties of a boricacid-water-sensitive polyvinyl resin size with new properties oflubricity, improved water resistance and improved yarn protection.

The above and other objects will become apparent in the course of thefollowing description of the invention.

The present invention-will be described particularly in relation to thefield of manufacture of full fashioned hosiery from nylon yarns since itis in this field that thecom'position has been found to have outstandingutility. The compositions of the invention are however useful in othertextile manufacturing operations in which yarns of nylon, vinylpolymers, rayon, cellulose esters, cotton, silk, wool or the like areem,- ployed.

Nylon yarns have been found to present a number of technical problems totextilemanufacturers and particularly tomanufacturers of full fashionedhosiery. Among the problems are tendencies for the yarn'to elongate andslip during knitting, making control of stitch and fabric lengthdiflicult, and a tendency for the fiat knitted fabric to curl at'the'edges, makingthe necessary seaming operation of the sheer fabricdifficult. Some of these problems are solved by the use of the boricacid-water-sensitive polyvinyl resin sizes described, for example,in-Patent Number 2,324,601 to spanagel. '--"Ihe combination of boricacid and water-sensitive polyvinyl resin is also referred to in theartas borated vinyl resin and borated polyvinyl alcohol (PVA). Sizes ofthis type produce a coating on the yarn which is sufiiciently adhesiveto reduce to 'a' substantial degree the objectionable tendencies toelongate and slip during knitting. 'The-boatlng'also stiffens the yarnand thus minimizes'the curling of the selvages. There are howeverseveralobjections to the heretofore known forms of these sizes. The boratedvinyl resin coating on the yarn is quite water-sensitive wherebyitftakes up water, softens and becomes subject to stripping, which isobjectionable mainly because itv fouls the knitting machines. Theborated vinyl resin coating does not adequately lubricate the yarn and aseparate yarn oiling operation is customarily required to protect theyarn and to assist good stitch formation and the maintenance of uniformtension. Another objection to the berated vinyl resin sizes is that theymust be compounded in water in a critical manner and from the separateingredients and they must, therefore, either be distributed as solutionsor made up from the components at the place of use. A dry mixture ofboric acid and, for example, polyvinyl alcohol is not readilydispersible in water presumably because the boric acid dissolves firstand the polyvinyl alcohol will not disperse smoothly in the boric acidsolution.

To overcome one or more of the objections to the simple boricacid-polyvinyl resin sizes there have been numerous proposals in the artto add various types of ingredients for modifying the characteristics ofthe resinous coating or to add special properties. Until the presentinvention, however, no way was known to overcome these objectionswithout introducing further dimculties, such as increasing thewater-sensitivity of the coating where the suggested additions arewatersoluble. Many of the proposals in the art for the addition ofwater-insoluble substances are of little or no use either by reason ofinability to introduce the suggested ingredients into aqueous solutionsof boric acid and the vinyl resins, or by reason of the loss of usefulproperties of the resin size when the necessary dispersing agents orsoivents are employed to include such ingredients.

In accordance with the present invention a textile sizing composition isprovided which comprises as active ingredients 2. water-sensitivepolyvinyl resin, boric acid, a. water-insoluble scourable waxy material(hereinafter referred to as a wax) which is incompatible with the resin,and a non-ionic water-soluble emulsifier for dispersing .the wax in anaqueous solution of the resin and boric acid. This composition has beenfound to have a number of unique properties. In the first place theknown beneficial properties of the borated vinyl resin composition areretained as to stiffening the yarn, anchoring the stitches duringknitting, and imparting snag resistance to the knitted products.Secondly, on the sized yarn the scourable wax is found to beincorporated into the sizing coating heterogenouslv and is found on thesurface of the coating andin places where the boric acid resin coatingis broken. This action of the water-insoluble scourable wax impartslubrication to the yarn without altering perceptibly the filmcharacteristics of the borated ,vinvl resin, reduces thewatersensitivity of the berated vinyl resin composition. and givesgreater protection to the yarn during knitting and subsequentoperations. A third and very important property of this new compositionis that it can be prepared in the form of a dry 3 mixture which can bemanufactured to exact specifications on a large scale and distributed tousers for dispersion in water for application to the yarn. In thedispersion of the dry composition no difllculty is experienced ingetting the borated vinyl resin into solution in the water. This isbelieved to be due to the coating of the vinyl resin particles with thescourablewax and emulsifier which in turn prevents lumping of the vinylresin when added to water.

The water-sensitive polyvinyl resins useful as yarn size ingredients arethe hydroxylated resins described in the said patent to Spanagel. Thepreferred resins are the commercial polyvinyl alcohols produced byhydrolyzing poylvinyl acetate, especially the low viscosity members ofthis group. These commercial polyvinyl alcohols may contain someresidual acetate radicals. Higher viscosity poylvinyl alcohols can beused only in dilute solutions but these can be used advantageously wheresizing is accomplished by multiple coating.

The scourable waxes that can :be used are water-insoluble materials thatare incompatible with the water-sensitive vinyl resins and that have awaxy consistency at temperatures to which a yarn is subjected duringknitting, weaving or other intended operation. The waxes must bescourable, that is, they must be sufliciently hydrophilic to be readilydispersible in water either alone or at least in the presence of a mildscouring agent, such as soap, to permit ready removal from the yarn atthe end of the manufacturing operation. Preferred scourable waxes arethose selected from the class consisting of (1) partial esters ofneutral polyhydroxylic organic compounds, with from 2 to 6 carbon atoms,and saturated fatty acids with from 16 to 30 carbon atoms; (2) diestersof hexldes and saturated fatty acids with from 16 to 30 carbon atoms;(3) waterinsoluble esters of polyoxyalkylene ethers of neutralpolyhydroxylic organic compounds with from 2 to 6 carbon atoms, andsaturated fatty acids with from 16 to 30 carbon atoms; and (4)waterinsoluble polyoxyalkylene ethers of partial esters of neutralpolyhydroxylic organic compounds with from 2 to 6 carbon atoms, andsaturated fatty acids with from 16 to 30 carbon atoms. Specific estersof group (1) are the ethylene glycol, propylene glycol, glycerol,erythritol, pentaerythritol, diglycerol, hexitol, hexitan, and hexide,partial esters of palmitic, stearic, margaric, camaubic, montanic andmelissic acids or mixtures of such acids. The preferred partial estersare the hexitan monoesters, especially sorbitan monopalmitate andsorbitan monostearate. Specific esters of group (2) are sorbide andmannide diesters of the named fatty acids, preferably sorbide or mannidedipalmitate or distearate. Specific esters of group (3) are the 16 to 30carbon atom fatty acids, tetra-, penta-, and hexaesters of apolyoxyethylene ether of sorbitol with an average of 6 oxyethylenegroups per molecule of sorbitol, the tetra and 'penta esters of thecorresponding polyoxyethylene ether of glucose, and the esters of thecorresponding polyoxypropylene ether of sorbitol or of glucose. Specificether-esters of group (4) are the polyoxyethylene ethers of hexitanmono-, di-, and triesters of fatty acids with from 16 to 30 carbon atomswherein the number of oxyethylene groups is insufiicient to render theethers water-soluble, as for example, the polyoxyethylene ethers ofsorbitan tristearate wherein there is an average of 16 oxyethylenegroups per molecule of sorbitan 4 tristearate. The polyoxypropyleneethers of hexitan fatty acid partial esters are further members of group(4) The class of scourable waxes that can be used according to theinvention comprises waxes with a considerable variation in meltingpoints, film hardness and dispersibility. The most desirable waxes fromthe standpoint of melting point and film hardness are relativelydiiilcult to disperse in water with the borated polyvinyl resin andtherefore require a large amount of water-soluble dispersing agents toproduce satisfactory dispersions. The dispersing agents have a tendencyto soften and weaken the'sizing coating when used in large proportionsothat it is desirable to keep the proportion of dispersing agent as lowas possible. It has been found possible to reduce materially, by 50% insome cases, the requirement for watersoluble dispersing agent byemploying as the scourable wax a mixture of two or more members of theclass of which one is a high melting, difficulty dispersible, hard waxand another is a more readily dispersible wax. All of the scourablewaxes in the mixture are valuable textile waxes and it is possible toformulate a mixture with optimum textile improving qualities and minimumrequirement for the water-soluble dispersing agent.

The water-soluble emulsifier for emulsifying the scourable wax in theboric acid-polyvinyl resin solution is a non-ionic organic compound, orpreferably a mixture of such compounds, with an aliphatic hydrocarbonportion of 10 to 18 carbon atoms and a polyoxyethylene portioncontaining a sufficient number of oxyethylene groups to render thecompound water-soluble. The linkage between the long chain hydrocarbonportion and the polyoxyethylene portion of the emulsifier may be director indirect, as for example of the ester type, RCOO(C2H4O) 11H, as wherethe hydrocarbon chain (R) is derived from a long chain fatty acid; ofthe ether type, RO(C2H40)nH, as where the hydrocarbon chain (R) isderived from a long chain fatty alcohol; or of the type wherein thehydrocarbon portion and the polyoxyethylene portion are both chemicallylinked through oxygen to a neutral organic coupling compound with from 3to 6 carbon atoms. Emulsifiers of the last named type are exemplified bycompounds of the types RCOQCsHtO (C2H40)nH and ROCaHaO (C2H40)nH, theCsHcO coupling portion being derived from propylene glycol or propyleneoxide. The coupling radical may also be derived from a polyhydricalcohol, with 3 or more hydroxyl groups such as glycerol, hexitols andhexitans. and in such cases the emulsifier may contain more than onelong' hydrocarbon radical and/or more than one polyoxyethylene chain. Itwill be apparent to those skilled in the art that emulsifiers of theclass contemplated by the invention can be prepared in various ways. Itwill also be apparent that, as in the case of most emulsifiers, moreefficient products result from the use of mixtures of related compoundssuch as occur in the production of emulsifiers from commercial grades ofmaterial and by the use of processes which produce not only the nominalreaction product but also quantities of related by-products. Forexample, the emulsifier for use in the preferred composition accordingto the invention, has the hydrocarbon radical derived from commerciallauric acid which contains, in addition to lauric acid, quantities offatty acids of lower and higher molecular weights. The polyoxyethyleneportion of the preferred emulsifier is introduced by reaction ofethylene v propylene glycol and commercial lauric acid in oxide and amonoester of the proportion of mols of ethylene oxide per mol of themonoester. This ethylene oxide reaction produces a wide distribution ofcompounds having different polyoxyethylene chain lengths. As understoodby the art the number of oxyethylene groups required to obtainwater-solubility for compounds containinglong chain hydrocarbon groupsvaries with the length, nature (saturated, unsaturated, hydroxylated,etc.) and number of such groups.

The sizing compositions according to the invention can be consideredconveniently to be composed of a boric acid-water sensitive polyvinylresin portion and a wax portion, the wax portion containing thescourable wax and the emulsifier. The relative proportions of the boricacid-resin portion and the wax portion may :be varied within wide limitsto obtain properties ranging from maximum stiffering, where the wax isat a minimum, to maximum lubrication where the wax is at a maximum. Theboric acid-resin portion and the wax portion can be mixed in virtuallyany proportions and aqueous dispersions of useful stability prepared.The viscosity of the aqueous dispersions increases as the wax contentincreases and this viscosity constitutes a limiting factor in many uses.The concentration of solids in the dispersion. can be varied to keepviscosity in a preferred range for some uses. For use in nylon yarnknitting sizes the ratio is preferably kept in the range 4.3 to 1.3parts by weight of 'borated vinyl resin to 1 part of the wax portion.The optimum ratio is 2.3 parts borated vinyl resin to 1 part wax forpresently accepted sizing and knitting techniques in the manufacture offull fashioned nylon hosiery.

The usual proportions of boric acid and watersensitive polyvinyl resincan be employed in the present invention. It is known and is describedfor example in the patent to Spanagel Number 2,324,601 that theseproportions can be varied to produce difierent characteristics of waterresistance, hardness, etc. In general proportions of 5 to 25% by weightboric acid based on resin are suitable. Some of the water-sensitivepolyvinyl resins will not tolerate as much as 25% boric acid, asdescribed by Spanagel, but the determination of this factor is verysimple to one skilled in this art. The limit of tolerance of aparticular resin for boric acid can be established by adding variousamounts of boric acid to an aqueous solution or dispersion of the resinand observing the quantity of boric acid that results in precipitationor gelling of the resin. The upper limit of tolerance of the resin forboric acid is the largest amount that can be added without causingpreci-pitation or gelling. In the preferred form of the presentinvention the resin is a polyvinyl alcohol with a saponification numberof about 140,

.a viscosity of 4 to 6 centipoises in 4% aqueous solution at C., andprepared by partially hydrolyzing polyvinyl acetate. With this resin thepreferred proportions of boric acid are 20 to by weight of the resin.

In the wax portion the relative amounts of scourable wax and emulsifiermust be such that the wax will be emulsified in the solution produced bydissolving the boric acid and the resin in water and so that theresulting emulsion will be sufii-ciently stable to permit properapplication to the yarn. For a sizing composition to be used on nylonyarn for hosiery manufacture the quantity of emulsifier should be keptto a minimum due to the softening effect of the emulsifier on the waxportion or the sizing coating. Furthermore the wax portion of the sizeshould be formulated to have a melting point sufliclently high to insurethat the wax will be solid under conditions of use. The preferred sizingcomposition employs a wax portion (scourable wax+emulslfier) with amelting point of about 37 C. as determined by a suitable modification oithe "Standard Method of Test for Melting Point of Petrolatum, A. S. T.M. designation D 127-30.

In the preferred sizing composition of the invention the wax portioncontains as the waterinsoluble scourable wax a mixture of a hexltanmonostearate, or monopalmitate, and a polyoxyethylene ether of a hexltantristearate in which there is an average of 16 oxyethylene groups permolecule of hexltan tristearate. This waxy poly- 'oxyethylene ether ismore readily water-dispersible than the hexltan monostearate orpalmitate and assists in its eanulsification thereby reducing the amountof emulsifier required. The emulsifier in the preferred composition is apolyoxy-= ethylene ether of propylene glycol monolaurate in which thereis an average of 15 oxyethylene groups per molecule of propylene glycolmonolau'rate. The specifically preferred composition for this waxportion of the size is 50% hexitan monostearate, or monopalmitate, 25%polyoxyethylene ether of hexitan tristearate (16 oxyethylene groups permolecule of hexltan tristearate) and 25% polyoxyethylene ether ofpropylene glycol monolaurate (15 oxyethylene groups per molecule ofpropylene glycol monolaurate) This specific composition is preferredbecause it gives sizing emulsions of excellent stability and the waxportion has a melting point of about 37 C. which insures that the sizingcoating will be solid under normal conditions for yarn processing. Thepreferred composition of the wax po tion of the size is susceptible ofvariation withi the ranges of 40 to 50% hexitan monostearate, ormonopalmitate, 22.5 to 33% polyoxyethylene ether of hexitan tristearate(16 oxyethylene groups per molecule of hexltan tristearate), and 22.5 to33% polyoxyethylene ether of propylene glycol monolaurate 15 oxyethylenegroups per molecule propylene glycol monolaurate), the total amountsconstituting The following specific examples illustrate the preparationand use of sizing compositions in accordance with the invention.

Example 1 The following materials were heated together in asteam-jacketed kettle to a temperature of 50 to 60 C. and stirred untilmelted and thoroughly mixed;

Pounds Sorbitan monopalmitate 50 Polyoxyethylene ether of sorbltantristearate containing .an average of 16 oxyethylene groups per moleculeof sorbltan tristearate 25 Polyoxyethylene ether of propylene glycolmonolaurate containing an average of 15 oxyethylene groups per moleculeof propylene glycol monolaurate 25 The mixture was then allowed to coolto room temperature.

In a separate container 95.5 lbs. of an aqueous solution of boric acidand polyvinyl alcohol were prepared as follows: 7.64 lbs. of thepolyvinyl alcohol were added to 55.73'lbs. of cold water with continuousstirring, and, after the polyvinyl alcohol was dispersed, thetemperature was raised to 70 C. Separately 1.53 lbs. of boric acid weredissolved with warming in 30.6 lbs. water. Both solutions were cooled to30 C. and the boric acid solution was added with stirring to thepolyvinyl alcohol solution. The polyvinyl alcohol used was prepared bypartially saponifying polyvinyl acetate and the product had asaponification number .of 140 and a viscosity of 4 to 6 centipoises in a4% aqueous solution at 20 C. The solution so prepared was heated withstirring to a temperature of 65 C. and to it were added 4.5 lbs. of thewax and emulsifier mixture prepared as in the preceding paragraph. Theresulting dispersion of the wax in the solution was then cooled to 26 C.while continuing the stirring and the viscosity of the dispersion wasadjusted to 120 seconds (Saybolt Universal at 78 F.) by the addition ofwater.

The above described dispersion was applied to yarn by a single sizingtechnique in which the yarn was wound from a spool or pirn over a sizingroll onto a drum. A 30-denier 10-filament 30-turn polyhexamethyleneadipamide yarn was sized by passing it at a speed of 750 yards perminuteover a rotating size roll dipping into a trough containing the sizedispersion. The speed of the size roll was adjusted to 9.0 R. P. M. andthe angle of contact of the yarn with the size roll was 5". Sizing wasdone at a room tempera ture of 78 F. and at an observed relativehumidity of About 5.0 to 5.5% of the size solids were applied based onthe weight of the yarn. After drying and aging, the yarn was conedwithout the application of oil or any other material. The sized yarn wasfound to knit well on a fullfashioned hosiery knitting machine and thesize adhered-well to the yarn even under conditions of high relativehumidity. The size was found to be readily removable by washing in hotwater which preferably contains a mild scouring agent.

Example 2 A water-dispersible dry composition containing ingredientscorresponding to'those described in Example 1 was prepared in thefollowing manner.

A No. 3 Lancaster mixer was charged with 13.7 lbs. of 'finely powderedboric acid and 68.5 lbs. of the poylvinyl alcohol described inExample 1. These ingredients were milled together in the mixer untilintimately mixed and then 35.9 lbs. of molten wax and emulsifiermixture, prepared as in Example 1, were added at a temperature of 45 C.Mixing continued until the mass was of uniform consistency and aftercooling to-25 to 30 C. the charge was transferred to a Stokes Granulatorin which it was granulated through a U. S. S. No. 10 wire screen. Theresultant product was collected and packaged.

A yarn sizing dispersion of the granular mixture prepared as describedwas made by gradually adding 12.5 lbs. of the granular mixture to 87.5lbs. of water heated to 65 C. with gentle stirring during the addition.The gentle stirring was continuedas the dispersion was cooled to 26 C.Thereafter, the viscosity of the dispersion was adjusted to 120 seconds(Saybolt Universal at 78 F.) by the addition of water. The dispersionwas used in sizing a nylon yarn in the manner described in Example 1 andthe yarn was knitted into full-fashioned hosiery with the same verysuccessful results.

Example 3 A yarn sizing dispersion was prepared and used as described inExample 1 with the variation that, in place of sorbitan monopalmitate inthe wax and emulsifier mixture of Example 1, sorbitan monostearate wassubstituted in the same proportion. The dispersion was prepared asreadily as in Example 1 and exhibited the same advantages on applicationto the yarn and in the subsequent manufacture of hosiery from the sizedyarn.

Example 4 A yarn sizing dispersion was prepared as described in Example1 with the variation that the wax and emulsifier mixtures of Example 1was replaced by a mixture of sorbitan monopalmitate and polyoxyethyleneether of propylene glycol monolaurate containing an average of 15oxyethy1ene groups per molecule of propylene glycol Eat sample 5 Adispersible dry composition was prepared with the ingredients describedin Example 2 but the proportions were varied in the following manner.

The Lancaster mixer was charged with 12.5 lbs. of finely powdered boricacid and 68.5 lbs. of the polyvinyl alcohol. When these ingredients wereintimately mixed 37 lbs. of the wax-emulsifier mixture were added in amolten condition at a temperature of 45 C. This composition wasgranulated and screened as in Example 2. The composition was dispersedin water to form a sizing composition as in Example 2 and the resultingdispersion was applied to nylon yarn. Subsequently the sized yarn wasknitted into fullfashioned hosiery with excellent results. The size ofthis example'has a lower proportion of boric acid to polyvinyl alcoholand also a higher proportion of wax to polyvinyl alcohol the effect ofwhich is to reduce slightly the stiffness of the sizing coatingdescribed in Example 2.

The dry sizing composition containing the borated vinyl resin, thescourable wax and the emulsifier can be prepared in any of theproportions and with any of the specific ingredients described above.This composition can be made up to precise specifications on a largescale and is avaluable article of commerce. The user of the compositionhas only to disperse it in water, adjust vicosity if necessary for hispurpose, and apply it to his yarn or fabric.

The wax portion of the size is also a valuable article of commerce andcan be prepared in alarge scale using any of the proportions andingredients described. The resulting wax is preferred by users whodesire to make up their own borated vinyl resin compositions or to varythe proportions of borated resin to wax.

The composition of the invention can of course be modifiednon-essentially by including coloring matters or the like. In theapplication of the sizes to yarns many variations can be made. Anchorcoatings of tannic acid or other substances can be used if desired butno such coatings have been found necessary up to the present time.Sizing may precede twisting of the yarns or may follow twisting or both.

In the course of the preceding description the terms solution, soluble,and dissolving have been used with reference to high molecular weightorganic compounds such as polyvinyl alcohol and polyoxyethylenederivatives but in accordance with the usual understanding in the artthese terms are employed to designate apparent solution recognizing thattrue molecular dispersion is not achieved in many instances. Also, theterms polyhydric and "polyhydroxylic are employed in the sense of morethan one hydroxyl group.

It will be apparent that many variations can be made without departingfrom the scope of the invention which is defined in the appended claims.

What is claimed is:

1. A textile sizing composition comprising a water-sensitive hydroxylicpolyvinyl resin; boric acid; a water-insoluble scourable wax which isincompatible with said resin and which consists of a compound selectedfrom the class consisting of (1) partial esters of neutralpolyhydroxylic organic compounds with from 2 to 6 carbon atoms andsaturated fatty acids with from 16 to 30 carbon atoms, 2) diesters ofhexides and saturated fatty acids with from 16 to 30 carbon atoms, (3)water-insoluble esters of polyoxyalkylene ethers of neutralpolyhydroxylic compounds with from 2 to 6 carbon atoms, and saturatedfatty acids with from 16 to 30 carbon atoms, and (4) water-insolublepolyoxyalkylene ethers of partial esters of neutral polyhydroxylicorganic compounds with from 2 to 6 carbon atoms, and saturated fattyacids with from 16 to 30 carbon atoms;

and a non-ionic water-soluble emulsifier for emulsifying said wax in anaqueous solution of said resin and said boric acid, said emulsifierconsisting of an organic compound with an aliphatic hydrocarbon portionwith from 16 to 18 carbon atoms and a polyoxyethylene portion containinga sufficient number of oxyethylene groups to render the compoundwater-soluble.

2. A textile sizing composition comprising polyvinyl alcohol; boricacid; a water-insoluble scourable wax which is incompatible with saidresin and which consists of a mixture of a hexitan monopalmitate. and awaxy water-insoluble polyoxyethylene ether of a hexitan tristearate; anda water-soluble polyoxyethylene ether of propylene glycol monolaurate asan emulsifier for emulsifying said scourable wax in an aqueous solutionof said polyvinyl alcohol and said boric acid.

3. A textile sizing composition comprising polyvinyl alcohol; boricacid; a scourable wax mixture containing a major proportion of a hexitanmonopalmitate, and a minor proportion of a polyoxyethylene ether of ahexitan tristearate wherein there is an average of about 16 oxyethylenegroups per molecule of hexitan tristearate: and a polyoxyethylene etherof propylene glycol monolaurate wherein there is an average of about 15oxyethylene groups per molecule of propylene glycol monolaurate as anemulsifier for emulsifying said scourable wax mixture in an aqueoussolution of said polyvinyl alcohol and said boric acid.

4. A composition for dispersion in an aqueous solution of polyvinylalcohol and boric acid to produce a textile sizing medium, saidcomposition consisting essentially of from 40 to 50% of a hexitanmonopalmitate, from 22.5 to 33% of a polyoxyethylene ether of a hexitantristearate wherein there is an average of about 16 oxyethylene groupsper molecule of hexitan tristearate, and

10 from 22.5 to 33% of polyoxyethylene ether of propylene glycolmonolaurate wherein there is an average of about oxyethylene groups permolecule of propylene monolaurate, the total amounts constituting 100%.

5. A dry composition adapted for mixture with water to produce a textilesizing medium, said composition comprising an intimate mixture of awater-sensitive hydroxylic polyvinyl resin; boric acid; awater-insoluble scourable wax which is incompatible with said resin andwhich consists a compound selected from the class consisting of (1)partial esters of neutral polyhydroxylic organic compounds with from 2to 6 carbon atoms and fatty acids with from 16 to carbon atoms, (2)diesters of hexides and saturated fatty acids with from 16 to 30 carbonatoms, (3) water-insoluble esters of polyoxyalkylene ethers of neutralpolyhydroxylic compounds with from 2 to 6 carbon atoms, and saturatedfatty acids with from 16 to 30 carbon atoms, and (4) water-insolublepolyoxyalkylene ethers of partial esters of neutral polyhydroxylicorganic compounds with from 2 to 6 carbon atoms, and saturated fattyacids with from 16 to 30 carbon atoms; and a non-ionic wa ter-solubleemulsifier for emulsifying said wax in an aqueous solution of said resinand said boric acid, said emulsifier consisting of a compound with analiphatic hydrocarbon portion with from 10 to 18 carbon atoms and apolyoxyethylene portion containing a sufficient number of oxyethylenegroups to render the compound water-soluble.

6. A dry composition adapted for mixture with water to produce a textilesizing medium, said composition comprising polyvinyl alcohol: boricacid; a water-insoluble scourable wax which is incompatible with saidpolyvinyl alcohol and which consists of a mixture of a hexitanmonopalmitate. and a waxy water-insoluble polyoxyethylene ether of ahexitan tristearate; and a water-soluble polyoxyethylene ether ofpropylene glycol monolaurate as an emulsifier for emulsifying saidscourable wax in an equeous solution of said polyvinyl alcohol and saidboric acid.

7. A dry composition adapted for mixture with water to produce a textilesizing medium, said composition comprising polyvinyl alcohol; boricacid; a scourable wax mixture containing a major proportion of a hexitanmonopalmitate, and a minor proportion of a polyoxyethylene ether of ahexitan tristearate wherein there is an average of about 16 oxyethylenegroups per molecule of hexitan tristearate; and a polyoxyethylene etherof propyleneglycol monolaurate wherein there is an average of about '15oxyethylene groups per molecule of propylene glycol monolaurate as anemulsifier for emulsifying said scourable wax mixture in an aqueoussolution of said polyvinyl alcohol and said boric acid.

8. A dry composition adapted for mixture with water to produce a textilesizing medium, said composition comprising from 4.3 to 1.3 parts byweight of a polyvinyl alcohol and boric acid mixture; and 1 part byweight of a mixture consisting of from 40 to of a hexitan monopalmitate,from 22.5 to 33% of a polyoxyethylene ether of a hexitan tristearatewherein there is an average of about 16 oxyethylene groups per moleculeof hexitan tristearate, and from 22.5 to 33% of a polyoxyethylene etherof propylene glycol monolaurate wherein there is an average of about 15oxyethylene groups per molecule of propylene 11 glycol monolaurate, thetotal of the percentages of a mixture of about 50% sorbitanmonopalmitate, about 25% polyoxyethyle'ne ether of sorbitan tristearatewherein there is an average of about 16 oxyethylene groups per moleculeof sorbitan tristearate, and about 25% polyoxyethylene ether ofpropylene glycol monolaurate wherein there is an average of aboutoxyethylene groups per molecule of propylene glycol monolaurate.

10. A textile sizing composition comprising P lyvinyl alcohol; boricacid; a water-insoluble scourable wax which is incompatible with saidresin and which consists of a mixture of a herdtan monostea'rate and awaxy water-insoluble polyoxyethylene ether of a hexitan tristearate; anda water-soluble polyoxyethylene ether of propylene glycol monolaurate asan emulsifier for emulsifying said scourable wax in an aqueous solutionof said polyvinyl alcohol and said boric acid.

11. A composition for dispersion in an aqueous solution of polyvinylalcohol and boric acid to produce a textile sizing medium, saidcomposition consisting essentially of from 40 to 50% of a hexitanmonostearate from 22.5 to 33% of a polyoxyethylene ether of a hexitantristearate wherein there is an average of about 16 oxyethylene groupsper molecule of hexitan tristearate, and 40 an average of about 15oxysthylene groups per molecule of propylene monolaurate, the totalamount constituting 100%.

12. A dry composition adapted for mixture with water to produce atextile sizing medium. said composition comprising polyvinyl alcohol;boric acid; a water-insoluble scourable wax which is incompatible withsaid polyvinyl alcohol and which consists of a mixture of a hexitanmonostearate and a waxy water-insoluble polyoxyethylene ether or ahexitan tristearate; and a water-soluble polyoxyethylene ether ofpropylene glycol monolaurate as an emulsifier for emulsifying saidscourable wax in an aqueous solution of said polyvinyl alcohol and saidboric acid.

13. A dry composition adapted for mixture with water to produce atextile sizing medium, said composition comprising from 4.3 to 1.3 partsby weight of a polyvinyl alcohol and boric acid mixture; and 1 part byweight of a mixture consisting of from to of a hexitan monostearate,from 22.5 to 33% of a polvoxyethylene ether of a. hexitan tristearatewherein there is an average of about 16 oxyethylene groups per moleculeof hexitan tristearate, and from 22.5 to 33% of a polyoxyethylene' etherof propylene glycol monolauratewherein there is an average of about 15oxyethylenegroups per molecule of propylene glycol monolaurate, thetotal of the percentages constituting GEORGE D. JEFFERSON. RICHARD D.FINE.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,297,135 Davis et al. Sept. 29,1942 2,300,074 Strain Oct. 27, 1942

1. A TEXTILE SIZING COMPOSITION COMPRISING A WATER-SENSITIVE HYDROXYLICPOLYVINYL RESIN; BORIC ACID; A WATER-INSOLUBLE SCOURABLE WAX WHICH ISINCOMPATIBLE WITH SAID RESIN AND WHICH CONSISTS OF A COMPOUND SELECTEDFROM THE CLASS CONSISTING OF (1) PARTIAL ESTERS OF NEUTRALPOLYHYDROXYLIC ORGANIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS ANDSATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, (2) DIESTERS OFHEXIDES AND SATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, (3)WATER-INSOLUBLE ESTERS OF POLYOXYALKYLENE ETHERS OF NEUTRALPOLYHYDROXYLIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS, AND SATURATEDFATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, AND (4) WATER-INSOLUBLEPOLYOXYALKYLENE ETHERS OF PARTIAL ESTERS OF NEUTRAL POLYHYDROXYLICORGANIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS, AND SATURATED FATTYACIDS WITH FROM 16 TO 30 CARBON ATOMS; AND A NON-IONIC WATER-SOLUBLEEMULSIFIER FOR EMULSIFYING SAID WAX IN AN AQUEOUS SOLUTION OF SAID RESINAND SAID BORIC ACID, SAID EMULSIFIER CONSISTING OF AN ORGANIC COMPOUNDWITH AN ALIPHATIC HYDROCARBON PORTION WITH FROM 10 TO 18 CARBON ATOMSAND A POLYOXYETHYLENE PORTION CONTAINING A SUFFICIENT NUMBER OFOXYETHYLENE GROUPS TO RENDER THE COMPOUND WATER-SOLUBLE.